Substituted (4-benzoyl-2-hydroxy phenoxy) alkyl thioalkanoic acid esters

ABSTRACT

Compounds are prepared having the formula   WHERE X is H, OH, R4, OR4 or halogen, R1 is hydrocarbyl of two to six carbon atoms, R2 is hydrocarbyl of one to four carbon atoms, R3 is hydrocarbyl of one to 22 carbon atoms. The compounds are useful as heat and light stabilizers for organic polymers, particularly alpha mono-olefin polymers.

Minimal Swims Psalm llnvemors lllagcmulln Il-llccllmillilelllmarllficmiwooiil; .llollm IF. Murmur, lbovrll; Arthur ll". llmcraimr,Cllmflmrmnllll; William P. mallow, imam, all! oi @lliiu Appl. No.$011,791

Filed lFllBlb. M, 115100 Patented Now. 110, will Assigncc (CarlimlcClaim]! Wm-lira, llnc.

@lliio SllJllllS (l-lllilENZQ/WZ-MWMUXY minnow) Mimi. 'riiionioic Acmmamas ll Il Qllaimma, No llllmwin iga US. iCil 260/070,

limit. Cl (C071: 1149/40 Walla oi 260/470 [56] llkciereum CM FOREIGNPATENTS 1,001 ,062 8/[965 England 260/470 Primary Examiner-James A.Patten Assistant Examiner-John F. Terapane Attorney-Cushman, Darby 8LCushman ABSTRACT: Compounds are prepared having the formula polymers,particularly alpha mono-olefin polymers.

The present invention relates to novel substituted benzophenones andtheir use as heat and light stabilizers.

it is an object of the present invention to prepare novel 2- hydroxybenzophenones.

Another object is to stabilize polymers and other materials to theaction of heat and light.

A more specific object is to stabilize hydrocarbon polymers against theaction oi" ultraviolet light.

Still further objects and the entire scope of applicability of thepresent invention will become apparent from the detailed descriptiongiven hereinafter; it should be understood, however, that the detaileddescription and specific examples, while indicating preferredembodiments of the invention, are given by way of illustration only,since various changes and modifications within the spirit and scope ofthe invention will become apparent to those skilled in the art from thisdetailed description.

lt has now been found that these objects can be attained by preparingcompounds of the following Formula l and using them to stabilizepolymers and other materials against heat and light, particularlyultraviolet light.

FORMULA I mooon where X is H, OH, 1R OR, or halogen, R, is hydrocarbylof two to six carbon atoms, it, is hydrocarbyl of one to four carbonatoms, lt is hydrocarbyl of one to 22 carbon atoms and R is hydrocarbylof one to 22 carbon atoms. Preferably the hydrocarbyl radicals are alkyl(including cycloalkyl) but they can be aryl or alkenyl for example. Thehalogen is preferably chlorine but can be bromide, fluorine or iodine.

Examples of compounds of the present invention within Formula l are2-hydroxy-4-(oxypropyl-El-thio lauryl propionate) benzophenone,2-hydroxy-4-(oxypropyl-3-thio lauryl acetate) benzophenone,2-hydroxy-4(orypropyl-Z'a-thio butyl propionate) benzophenone,2-hydroxy-3-methyl-4-(oxypropyl-B-thio lauryl propionate) benzophenone,2-hydroxyl-(onyQ-rnethylpropyl-thio octadecyl propionate) benzophcnone,2-hydrorry-4(oxypropyl-Z-thio butyl acetate) benzophenone,2-hydroxy-4-(oxyethyl-Z-thio methyl acetate) benzophenone,2-hydroxy-4-(oxyethyl-3-thio methyl propionate) benaophenone,2-hydroxy-4-(oxybutyl-Z-methyl- Z-thio docosyl acetate) benzophenone,Z-hydroxyl-(oxypropyl-3-thio docosyl propionate) benzophenone,Z-hydroxy-4-(oxyethyl-3-thio methyl pyruvate) benzophenone, 2-hydroxy'4-(oxyethyl-3-thio dodecyl propionate)-2'-hydroxy benzophenone,2-hydroxy-4-(oxypropyl-3-thio dccyl propionate)-2'-hydrony benzophenone,2-hydroxy-4-(oxyethyl-3-thio dodecyl propionate)-4'-chloro benzophenone,2-hydroxy- -l-(oxypropyl-Z-thio octadecenyl acetate)-4'- bromobenaophenone, 2-hydroxy-4-(oxypropyl-Z-methyl-Ilthio lauryl propionate)benzophenone, Z-hydroxy-l-(oxypropyl-Z -methyl-2-thio lauryl acetate)benzophenone, 2- hydroxy-4-(oxyethyl-3-thio octyl propionate)benzophenone, 2-hydroxyl-(oxyethyl-El-thio dodecyl propionate)-5-chlorobenzophenone, 2-hydroxy-l-(oxyhexyl-3-thio ethyl propionate)benzophenone, 2-hydroxy-4-(oxypropyl-4-thio allyl butyrate)benzophenone, 2-hydroxy-4-(oxyethyl-2-thio cyclohenyl acetate)benzophenone, Z-hydroxy-d-(oxypropybii -thio phenyl propionate)benaophenone, 2-hydr0xy-4 -(oxypropyl-S-tlrio-p-tolyl valet-ate)benzophenone, 2-hydroxy-4- propionate) benzophenone,2-hydroxy-l-(oxyethyl-Z-thio o benaophenone,2-hydroxy-4-(oxypropyl-3-thio dodecyl)-3'- tluoro benzophenone,2-hydroxy-4-(oxyethyl-3-thio dodecyl propionate)-3'-hydroxybenzophenone, 2-hydroxy-4-(oxypropyl-Z-thio octadecyl acetate)2'-methoxy benzophenone, Z-hydroxy- 4-(oxypropyl-3-thio dodecylpropionate) butoxy benzophenone, 2-hydroxy-4-(oxypropyl-3-thio phenylpropionate) 2'-octadecoxy benzophenone, 2-hydroxy-4-(oxypropyl3-thiododecyl propionate)-4'-docosyl benzophenone,2-hydroxy-4-(oxycthyl-3-thio dodecyl propionate)-2'-methyl benzophenone,Z-hydroxyA-(oxyethyl-Z-thio sec. butyl acetate)-2'-hexyl benzophenone,2- hydroxy-4-(oxypropyl-3-thio cyclopentyl propionate) 4'-octadecylbenzophenone, 2-hydroxy-4-(oxybutyll-thio decenyl butyrate)-5'-docosylbenzophenone, 2-hydroxy-3-methyl-4- (oxyethyl-Z-thio dodecylacetate)-2'-cyclohexoxy benzophenone, 2-hydroxy-4-(oxypropyl-2-thiododecyl acetate)-2'-phenoxy benzophenone, 2-hydroxy-44oxypropyl- 3-thiododecyl propionate )--2'-alpha naphthoxy benzophenone.

The compounds of the present invention can be used to protect thefollowing types of polymers from degradation by light (e.g., ultravioletlight) or heat, vinyl chloride polymers includ ing polyvinyl chloridesand copolymers of vinyl chloride with other materials such as vinylacetate, vinylidene chloride, acrylonitrile, maleic anhydride, vinylstearate, ethyl acrylate, methyl acrylate, octyl acrylate, etc.,polyvinylidene chloride, chlorinated polyethylene, chlorinatedpolybutadiene, polystyrene, impact polystyrene, e.g. a mixture ofpolystyrene with 5 percent butadiene-styrene copolymer,styreneacrylonitrile-butadiene terpolymer (ABS) polycarbonates, e.g.bisphcnol A polycarbonate, polyesters, e.g. polyethylene terephthalate,acrylic and methacrylic polymers, cg. ethyl acrylate, methyl acrylate,butyl acrylatc, methyl methacrylate, epoxies, e.g. bisphenolA-epichlorohydrin, polyolefin rubbers, e.g. polybutadiene, poly cisisoprene, butadiene-styrene copolymer, butadiene-acrylonitrilec-opolymer, alpha-monoolefin polymers and copolymers (particularlypolymers of alpha mono-olefins having 2 to 10 carbon atoms) e.g.polyethylene, polypropylene, polyisobutylene, butene-l 3-methylbutene-l, hexene-l, heptene-l, octene-l, decene-lethylene-propylene copolymer, ethylene-butene-l copolymer,ethylene-propylene-cyclo-octadiene terpolymer,ethylenepropylene-norbornadiene terpolymer, etc. There can also bestabilized gasoline, mineral oil and fatty materials of animal orvegetable origin, e.g. linseed oil, menhaden oil, lard, cottonseed oil,partially hydrogenated cottonseed oil, corn oil, peanut oil, palm oil,cod liver oil, coconut oil, butter, beef tallow, etc.

Unless otherwise indicated all parts and percentages are by weight.

The compounds of Formula ll can be added in an amount of 0.001 to 10percent of the material being stabilized but preferably are used in anamount of 0.[l to 1 percent.

The products of the invention can be used alone or with other adjuvantssuch as mold release agents, cg. zinc stearate and aluminum stearate,nickel complexes, hindered phenols, thioesters, etc.

Thus there can be used 0.05 to 5.0 percent based on the polymer ofnickel complexes such as the nickel dodecyl amine complex of 2,2'-thiobis(p-t-octyphenol), nickel butylamine complex of 2,2'-thiobis(p-t-octylphenol) and other nickel complexes such as those shown inUS. Pat. Nos. 2,971,940; 3,006,886 and 3,218,294.

ll-lindered phenols can be added in an amount of 0.01 to 10 percent ofthe polymer. Examples of such phenols include di(t-butyl) p-cresol,4,4'-thio bis(6-t-buty1-m-cresol), 2,2-

methylene bis( l-rnethyl-tS-t-butylphenol 2-t-butyl-4- decyloxyphenol,2-t-butyl-4-octadecyloxy phenol, 4,4- methylenebis(2,6-di-t-butylphenol), bis [o-( 1,1,15,3-

tetramethylbutyl) phenol] sulfide, bis(p-octylphenol) sulfide, etc.

Thioesters can be added in an amount of 0.005 to 10 percent of thepolymer. Examples of such thioesters include dilauryl beta-thiodipropionate, dioctadecyl beta-thio dipropionate, dioleyl beta-thiodipropionate.

The substituted benzophenones can be prepared in several different ways.

Method A An appropriate dihydroxybenzophenone is reacted with achloroalltylthioalltanoic acid ester in the presence of alkali and analkali metal iodide, e.g. sodium iodide or potassium iodide. Thus toprepare 2-hydroxy-4-(oxypropyl-B-thiolauryl propionate) benzophenone theequation is OH I H C 214 grams (1 mole) of dihydroxybenzophenone, 116grams (1.1 mole) of anhydrous sodium carbonate, 16.6 grams (0.1 mole) ofpotassium iodide, 350.5 grams (1.0 mole) of lauryl-3-chloropropylthiopropionate (prepared as set forth below) and 1 literof acetone (solvent) were heated for 5 hours at 150 C. in an autoclave.After the reaction the mixture was,

cooled, added to 1 liter of water and the acetone stripped bydistillation with some water. The water later was separated and theremaining product was crystallized from isopropanol. The yield of2-hydroxy-4-(oxypropyl-3-thio laurylpropionate) benzophenone was 503grams (95 percent of theory), MP. 6264 C.

in this general procedure the reaction time employed was 5-10 hours butthis can be varied. Similarly, crystallization can be accomplished fromhexane or other hydrocarbon solvents rather than isopropanol. The yieldsin general were 85-95 percent.

To make other compounds within the invention in place oflauryl-3-chloropropylthiopropionate, there can be used lauryl-3-chloropropylthioacetate, lauryl-2-chloroethylthioacetate,lauryl-2-chloroethylthiopropionate, phenyl-B chloropropylthiopropionate,methyl-3- chloropropylthioacetate, butyl-3-chloropropylthioacetate,docosyll-chlorobutylthioacetate, octadecenyl-3- chloropropylthioacetate,cyclohexyl-2- chloroethylthioacctate, benzyl-3-chloroethylthiopropionateand the like.

These intermediate chlorothioester esters are prepared in 95-100 percentyields by reacting mercaptoesters with chlorobromohydrocarbons accordingto the following equation, for example,

ClCH Cl-lI ClihBrrhlsCll COOC l-l -l-Na co ClCl-ll CH SCHCOOCJ-lQbZNaBH-NaHCO For example the 3-chloropropyl laurylthiopropionate employed in the representative example for Method A wasprepared as follows.

157.5 grams (1 mole) of l,3-chlorobromopropane, 274

grams (1 mole) of lauryl mercaptopropionate, 122.2 grams (1.2 mole) ofsodium carbonate and 1 liter of acetone were mixed and heated underreflux for 16 hours. The mixture was added to 3 liters of water and theupper layer was separated and washed with 1 liter of water and driedwith sodium sulfate. The yield of lauryl-3-chloropropylthiopropionatewas 332 grams or 95 percent of theory. The product was a colorless oil.The structure was substantiated by infrared data and sulfur and halogenanalyses.

Method B An appropriate mono allyl or vinyl ether of adihydroxybenzophenone is reacted with a mercaptan alkanecarboxylic acidester in the presence of an alkali metal or alkoxide catalyst. Theproduct obtained was recrystallized from isopropanol or hexane and theyield was 60-90 percent of theory.

The equation for a typical reaction is In a specific example there wasprepared 2-hydroxy-4-(oxypropyl-3-thio-lauryl acetate) benzophenone byreacting 260 grams (1 mole) of lauryl thioglycolate (HSCH COOC IL with260 grams (1 mole) of 2-hydroxy-4-allyloxybenzophenone in 1 liter oft-butanol containing 2.3 grams (0.1 mole) of sodium. The reaction wascarried out by heating under reflux for 6 hours. The product wasisolated by cooling and filtering the crystalline solid and byrecrystallizing from hexane. The yield was 415 grams percent of theory),M.P. 39-4l C.

Method C This method is a modification of method B wherein instead of acatalyst irradiation with ultraviolet light is used to achieve thereaction of the allyl or vinyl ether of a dihydroxybenzophenone with amercaptan alkanecarboxylic acid ester. A quartz reaction vessel isemployed to insure maximum light transmission. The reaction ispreferably carried out in an inert solvent, e.g. a hydrocarbon such asbenzene, toluene, xylene, aromatic naphtha, hexane, petroleum ether,etc. yields of 50 to percent have been obtained.

ln a specific example there was prepared 2-hydroxy-3-methyl-4-(oxypropyl-3-thio lauryl propionate) benzophenone by reacting277 grams (1 mole) of 2-hydroxy-3-methyl-4-allyloxybenzophenone with 274grams (1 mole) of lauryl mercaptopropionate (HSCH CH CO0C, H, in 1 literof benzene and irradiating for hours with an ultraviolet lamp.Specifically there was employed a quartz lamp which was a G. E. lamp,Code H 100 PSP 38.4. The yield of 2-hydroxy-3-methyl-4-(oxypropyl-B-thio lauryl-propionate) benzophenone was380 grams (70 percent of theory), a crystalline solid MP. 70-73 C.

1n the following tests the compound 2-hydroxy-4-octoxybenzophenone wasemployed simply as a comparison. It was particularly surprising that thecompounds of the invention not only imparted to the polymersultraviolet-light stability but Z-hydroxy-4-octoXybenzophenone.

TABLE 1 K values M.P., coeificient in Compound Name Method of preparingC. isopropanol 1 2-hydroxy4-oct0xybenzophenone 49-50 52 (23 22-hydroxyA-(oxypropyl-Z-thiolauryl A or B 62-64 20.7 (288 111p)propionate) benzophenone. 3 i. 2-hydr0xy-4-(oxypropyl-Z-thiolauryl A orC 29-41 29.7 (2 7 acetate) benzophenone. 4Z-hydroxyd-(oxypropyl-B-thiobutyl A Llquid 36.8 (238 mp) propionate)benzophenone. 5 2-11ydroxy-K-methyl-4-(oxypropyl-3thio C or A 70-73 30.1(28 111g) lauryl propionate) benzophenone.

The compounds were used to stabilize polypropylene as p a shown in table2. in table 2 the concentrations of compound are per 100 parts oipolymer (phr); AA designates an accelerated aging test of thepolypropylene in the form of SO-rnil y nyl rm 103 EP) |oo om film in acirculating air oven at 150 C; and Weatherorneter in- 123; g wvlmeimpact 3 dicates an tdu'aviolet-lipht test an Atlas twin-arc Model mmAce p.12 (imam madman 15 m DMC-llIlR using the procedure in ASTMDesimration E-42-6 Dlbutylfin bin y u ycolme) 2 parts 5 Advuwux I35 0.75parts 2-hydroxy-4(oxypropyl-3-thio luuryl The compounds were milled intothe polymer. propionnte) benzophenone o5 Pam TABLE 2 in acceleratedulurmriolet-light tests tor a period of 24 hours, 25 in the formulationoi table 4, the compound of the invention gave a much more light-stableproduct than either a formula- Compound cmwlm'im g tion with noultraviolet-light stabilizer or a stabilizer contain- I in? 2; 3a ingthe compound 2-hydroxy-4-octoxybenzophenone. 2 as was 220 The compoundsof the present invention are also useful as 3 MD was 2 light filters forsuntan creams and cosmetic pre arations and 4 in moo zoo as an additiveto protect material from deteriora on due to ul- 5 m a g: fig travioletradiation. in an LD study with rats, the toxicity of 2- 3:52hydro:ry-4-( oxypropyl 3-thio lauryl propionate) 1 are We beuzophenonewas extremely low being greater than 20 grams per lrilo of body weight.(in compoundl What is claimed is:

J A s nior-misdeeds formula (b) distcuryl thiodipropionatc 0H 0 Compound2 ot' the above table, it will be observed, is better ORISRZCOOR1 than acombination of Z-hydroxy-A-octoxybenzophenone and distearylthiodipropionate by a factor otat least it "M- W. X1

in an accelerated oven aging test, at 150 0. there was employed a basicmixture oi 60 percent polypropylene (Diamond Awhere Shamrock 4 meltflow) and 40 percent asbestos (Aplen 101), X, or X is H, Oil. 1R. 01R.or halogen, R is alkylene of two to to lOO parts of the basic mixturethere was added the insix carbon atoms, R is alltylene one to fourcarbonatoms, R dicated parts of the formulations set forth in table 3.1S hydrocarbyl of one to 22 carbon atoms and R. 18 alkyl or hydrocarbonaryl of one to 22 carbon atoms.

2. A compound according to claim ll wherein R, is alitane of TABLE 3 twoto three carbon atoms and R is of one to two carbon atoms.

3. A compound according to claim 2 wherein X is Accelerated 0ven AgingTests hydrogen.

4!. A compound according to claim 3 wherein X is 3 g hydrogen. p s. Acompound according to claim a wherein a. is alltyl. D rd OJ 5 17 r 6. Acompound according to claim 3 wherein X is chloro or r znoi sii 0, 1lower alltyl and R is alkyl. (Hindcrcd condensed phenol) '7. A compoundaccording to claim 2 wherein X is hydroxy Dislerdflp 0.15 or chloro andX is hydrogen. gf i g Q05 h. A compound according to claim 11 which is2-hydroxy-4- 2-l ydroxy-4-octoxybonz0phcnone 0.50 yp py y pxtopionate')benzoPhelzlone' 2-Hydroxy-4-(lauryl 07typropy|-3- 9 A compound accordingto claim 11 which 13 2-hydroxy-4- lhiopmpiflnm)bmmvlmmm(oxypropyl-B-thiolauryl acetate) benzophenone.

iii. A compound according to claim l which is 2-hydroxy-3- v V V V ,7 WW methyl-4-(oxypropyl-3-thiolauryl propionate) benzophenone. Thecompounds were also tested as ultraviolet-light stabil- A compolfndaccording Claim 11 which is l' y' izers in a polyvinyl chloridecomposition. Thus a sheet was l'p py l P P m phen neprepared of thefollowing formulations: o o u it i

2. A compound according to claim 1 wherein R1 is alkane of 2 to 3 carbonatoms and R2 is of 1 to 2 carbon atoms.
 3. A compound according to claim2 wherein X1 is hydrogen.
 4. A compound according to claim 3 wherein X2is hydrogen.
 5. A compound according to claim 4 wherein R3 is alkyl. 6.A compound according to claim 3 wherein X2 is chloro or lower alkyl andR3 is alkyl.
 7. A compound according to claim 2 wherein X1 is hydroxy orchloro and X2 is hydrogen.
 8. A compound according to claim 1 which is2-hydroxy-4-(oxypropyl-3-thiolauryl propionate) benzophenone.
 9. Acompound according to claim 1 which is2-hydroxy-4-(oxypropyl-3-thiolauryl acetate) benzophenone.
 10. Acompound according to claim 1 which is2-hydroxy-3-methyl-4-(oxypropyl-3-thiolauryl propionate) benzophenone.11. A compound according to claim 1 which is2-hydroxy-4-(oxypropyl-3-thiobutyl propionate) benzophenone.